Process for the manufacture of cyclic sulphur compounds such as thiophene and its derivatives



Patented Sept. 13, 1932 UNITED STATES ERIC '1'. HESSLE, or nooxronw,ILLINOIS, AssIeno'n ro'rnrornnnnrnonuors coin- IPANY, CHICAGO, ILLINOIS,

A CORPORATION OF ILLINOIS rnoonss non THE MANUFACTURE or exotic SULPHURcoivrrouivns sucrr AS THIC- rnnnn AND rs nnnrvnrrvns No Drawing.Application filed July 28,

This process relatesto the manufactureof products for pharmaceuticalpurposes containing thiophene and its derivatives, or other hydrocarbonsof a cyclic. nature having, a sulphur atomwdirectly on the ringstructure.

In carrying out my process I preferably employ a crude oil containinghydro carbon sulphur compounds and over fifty percent (50%) ofunsaturated hydrocarbons and having an asphaltic base. The oil is firstsubjected to an ordinary distillation process. The first fractions oflower boiling points consisting of gasolme and kerosene are, in the casewhere'crude oil is employed, collected separately and not used formanufacture of cyclic sulphu'rcompounds for the reason that they areusually saturated. In the case where synthetic oils are used, which arecommercially produced by cracking processes, the lighter fractions maybe used for this process. Fractions dlstilling after the kerosenefraction, and consisting of gas oil, spindle oil, light and heavylubricating oils, are the base mater als for this process, while theresidue remaining n the still and comprising mainly asphalt isdiscarded. The base materials thus obtained are placed in a vacuum stilland heated slowly in the presence of an oxygen containing compound ofthe iron group. Of these substances an iron oxide has'been found veryeffective and economical. As the reaction products formed in the vacuumstill are highly corrosive, the still, vapor lines and condensers arepreferablym'ade ofcastiron'.

Any iron compound, as .long as it-is a combination of oxygen, orhydroxyl with iron, can be used. I have found that the most suitableform of applying the iron oxide for this particular process is in theform of long and light iron turnings or shavings which have beensubmitted to the action of gasoline and a diluted acid and afterwardsexposed to the air for several weeks. The turnings are then placed incast iron baskets and hung in the vacuum still. Insome instances I havefound that the oxidation of the internal walls of the still, whichoccurs in 1927. Serial No. 209,185.

my process, will provide suflicientironjoxide for the purpose described.h

The still containing the oil to be treated is first heated up withouttheapplication of a vacuum and maintained at ajtemperature around 200degrees C. for two hours. I hGn add very slowly to the contents of thestill a thin paste of flowers of sulphur, powdered iron oxide and oil,at the same time constant ly maintaining the temperature between 200 and250 degrees'C. The basket of iron turn ings may now be removed from thestill. The vacuum-may then be slowly: applied throughout the systemuntil it reaches twen ty-eight to twenty-nine inches of vacuum, whichismaintained during the remainderl'of the distillation process. The fireis increased gradually and distillation is started and continued. Atthesame timesuperheated steam atapproximately 300 degrees is slowly blowninto the bottom of the still. The first part of the distillation isaccompanied by, the formation.ofhydrogen-sulphide gas, which is absorbedto a small extent by the lighter, distillates, giving them a bad odor..This odor may be eliminated by heating these distillates. The heavierbodies have no or a very slight odor.

The sulphur compounds having cyclic structures with sulphur directlyonthe ring are not elfected by this treatment, and they will be foundunchanged after reaction has taken place, but the mercaptans andhydrocarbon sulphides of open or cyclic structure are converted intometal salts and the metal salts being unstable under heatare decomposedforming metal sulphides, and, at the same time, 'molecular sulphur istaken into the hydrocarbon molecule, formin V to a great extent sulphurcompounds 0 cyclic nature, such as thiophene or its derivatives. Anotherreactiontakes place, as follows The molecular sulphur at a temperatureof over 200 degrees C. has a tendency to-form sulphides by entering thehydrocarbonmole cule on an unsaturated or double bond. These sulphidesare not very stable, having a tendency to form polymerizationlproductaand finally being converted into heavy asphaltic masses.However, in the presence of a 7 too oxide, metal salts are formedinstantly and 7 bearing sulphur in the ring structure which consistsinsubmitting hydrocarbon I sul-. phur compounds containing sulphur I innon-cyclic combinations to the action of an oxygen containing compoundyof; the iron group and molecular sulphur under heat and distilling inthepresence of a vacuum and super-heated steam. for the manufacture ofor- "2. A process 7 game sulphur compounds of cyclic nature whichconsists in submitting hydrocarbon sulphur compounds of straight chainstructure to the action of an oxygen containing compound'ofa-the irongroup and molecular sulphur under" heat and distilling in the presenceora' vacuum and superheated steam. 3. A processfor the manufacture oforganic sulphur compounds of cyclic nature from ,a hydrocarbon oilcontaining sulphur compounds: which consists in eliminatingv-l'igh-t'hydrocarbons of low boiling point and heavy residues of highboiling'point from said hydrocarbon oil, submitting theremaining'lfractions to the action of an oxygen conc d bons withmolecular sulphur in the presence of an oxygen containing metal compoundthe taining compound of the iron group, an molecular sulphur under heatand distilling the mass in the presence of a vacuum and superheatedsteam.

4. A process for the manufacture of organic sulphur compounds of cyclicnature which'consists in submitting a body of hydrocarbon oilhavingunsaturated; constituents to the action of an oxygen containingcompoundof the irongr'oup and molecular sul phur under heat and distillingthemass in the presence of a vacuum and superheated steam.

5; A process for the manufacture of organic sulphur compounds of cyclicnature which consists in distilling a hydrocarbon oil having anasphaltic base and containing hydrocarbon sulphur compounds, separatingout the lighter oils and asphaltic residue, sub-- mitting the remainingfractions to the action of anoxygen containing compound of the irongroup, and molecular sulphur under heat and distilling the mass inthe'presence of a vacuum and superheated steam.

' 6. A process for the manufacture oforganicsulphur compounds of cyclicnature which consists in submitting a hydrocarbon oil containing,sulphur compounds and unsaturated constituents to the action of heat inthe presence of an' oxygen containing compound of the iron 'group at anelevateditemperature, adding molecular sulphur and maintaining thetem'peraturebetween 200and V 7 7. A-process organicsulphur compounds ofcyclic nature of Ju1 ,-1 27.

250 degrees C. progressively applying a vacuum to the mass thus formedup toapproximately twenty-nine inches, and continuing the distillationof said mass in the presence of said vacuum and superheated 'steam.-'- Ww for the manufacture of organic sulphurcompounds of cyclic nature whichconsists in submitting a hydrocarbon oil containing hydrocarbon sulphurcompounds and unsaturated constituents to the action of heat in "thepresence of an oxygen containing compound-of the iron group, addingmolecular-sulphur, applying-a vacuum to the mass thus formed anddistilling said mass in the presence of saidivacuuin and'superheatedsteam. v. 1 v

8. A process for the manufacture oforganic sulphur compounds of cyclicnature which consists in submitting'a hydrocarbon oil containinghydrocarbon sulphur compounds and unsaturated constituents to the actionof h eat'in thepresenc-e of an oxygen containing compound of the irongroup adding a mixture of molecular sulphur, oil and powdered metaloxide of the iron group, applying a va'cuumto themassthus formed anddistilling saidmass in thepresence of said vacuum and superheated steam.j Y 9. In a-process for the preparation of hydrocarbonso-f a cyclicnature containing sulphur in the ring, the step which comprises 7heating unsaturated open chain hydrocarmetal constituent of whichbelongs to the iron group 1 10; The. process of preparing hydrocarbonsof acyclic nature containing sulphur in the ring, which comprisesheating unsaturated'open chain hydrocarbons free from asphaltic residueswith molecular sulphur in the presence of an iron oxide and distillingfree from asphaltic residues and lower boil- 1 ing fractionswithmolecular sulphur in the presence of an oxygen containing metalcompound, the metalconstituent of which be-' longs to the iron group,maintaining a tem-.

perature during the reaction of about 200C. to 250 C. and distillingthemass under a relatively high vacuumin the presence of an inert gas. g. Vv

, Signed a, Chicago, Illinois, this 29a; as

E inor. HESS-LE.

